JP2001504151A - Method for producing rigid and flexible polyurethane foam - Google Patents

Abstract

  (57) [Summary] A method for producing rigid and flexible polyurethane foams by reacting a polyisocyanate with two kinds of polyols under foam forming conditions, wherein the polyisocyanate is a compound containing a primary, secondary or tertiary amine. The method of reacting with the polyol in the absence. A flexible foam which did not show a major glass transition temperature between -100 ° C and + 25 ° C was obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION                Method for producing rigid and flexible polyurethane foam   The present invention relates to a method for producing rigid and flexible polyurethane foam.   Conventional flexible polyurethane foams are widely known. Such foams are Relatively high resilience (ball rebound), relatively low modulus, relatively high sag Exhibit a relatively low hysteresis loss. In addition, such a form A major glass-rubber transition occurs below ambient temperature, typically in the temperature range of -100 ° C to -10 ° C. Show. Generally, relatively high molecular weight polyethers and polyesters are added to such foams. When terpolyols are applied, the glass transition temperature below ambient temperature (Tg^sInvite) . These polyether and polyester polyols are often This is called a fragment. Tg^sAbove is the isocyanate-derived urethane / urea class The foam is allowed to soften until softening and / or melting of the Exhibit typical soft properties. This softening and / or melting temperature (Tg^hAnd / or T m^h) Often coincides with the onset of thermal decomposition of the polymer segment. Soft poly Tg of polyurethane foam^hAnd / or Tm^hIs generally above 100 ° C, often 2 It can even exceed 00 ° C. Tg^sNow, the sudden decrease in elastic modulus of flexible foam Is found. Tg^sAnd Tg^h/ Tm^hThe elastic modulus is completely constant even when the temperature rises But Tg^h/ Tm^hThen, again, a substantial decrease in modulus can occur. Tg^sThe presence of One way to express is to use Dynamic Mechanical Thermal Analysis nalysis) (DMTA measured according to ISO / DIS 6721-5) at temperatures between -100 ° C and + 25 ° C. The ratio of the storage elastic modulus E ′ may be measured. Conventional flexible polyurethane foam about, The ratio is at least 25.   Tg by DMTA (ISO / DIS 6721-5)^sAnother feature of the conventional soft polyurethane For tamform, over the temperature range of -100 ℃ / + 25 ℃Maximum value of the ratio (tan_δmax) Generally varies from 0.20 to 0.80. The Young's loss modulus E "is also measured by DMTA (6721-5).   Conventional flexible foams, in the presence of blowing agents, may optionally contain limited amounts of relatively small molecules. The amount of chain extender and crosslinker further used, and optionally the catalyst, surfactant Additives such as antioxidants, flame retardants, stabilizers and antioxidants And relatively high molecular weight isocyanate-reactive polymers, often polyester It is produced by reacting with a ter or polyether polyol. Relatively Higher molecular weight isocyanate-reactive polymers generally have the highest weight fraction of the foam. Means minutes. Such flexible foams can be one-shot, pseudo- or semi-prepo It can be produced by a remer or prepolymer process. Such flexible foams Can be molded into foam or slabstock foam, furniture and automobiles As a cushioning material for seats and mattresses, as a carpet backing, Can be used as hydrophilic foam of diapers, as well as packaging foam You. Furthermore, it can be used for soundproofing applications, for example for sound insulation. These conventional soft fonts Examples of the prior art are disclosed in European Patent Nos. 10850, 22617 and 111121. No. 296449, No. 309217, No. 309218, No. 392788 and No. 442631 Is mentioned.   Polyisocyanates have high isocyanate functionality and the high molecular weight used Under the condition that the amount of polyols is small and the functionality of the crosslinking agent is high, Is produced in a similar manner.   PCT WO92 / 12197 acts as a blowing agent and cell-opener in a mold Energy obtained by reacting a polyurethane foam formulation containing water Ruggie-an absorbent, open-cell, water-foamed rigid polyurethane foam. The cured foam is about 32 ~ 72kg / m^ThreeMolded density and 70psi Crush strength (cmsh strength) to maintain a constant deflection of 10 to 70% under less than load This form is disclosed. This form has minimal return or hysteresis. I do.   UK Patent No. 2096616 discloses a directional softened, rigid, closed-cell plastic Disclose the lock form. This rigid foam is used, for example, for pipes-insulation Be flexible to be. Cells must remain independent.   U.S. Pat. No. 4,298,983 states that foam recovers to 50-66% of its original thickness By compressing the foam with closed cells (closed cells) to a degree A manufactured sound absorbing material is disclosed. Upon compression, the cells break and the foam becomes soft and soft. Resilience; felt can be replaced. This disclosure primarily relates to poly It relates to a carbodiimide foam.   European Patent No. 561216 describes a ratio of the length of the major axis to the minor axis of 1.2 to 1.6 and a density of 15 to 45 kg / m.^Three Anisotropic cell, the cell being crushed in the plate thickness direction, improved heat insulation Disclosed is the manufacture of a foam board having properties. This disclosure is actually About Renboard.   European Patent No. 641635 has a density of 17-30 kg / m^ThreeA board of 60-90 of its original thickness % MN / m by crushing at least twice^ThreeHas the following dynamic rigidity A method for manufacturing a foam board is disclosed. The use of closed-cell polystyrene preferable. In the examples, the crushed polystyrene foam is not crushed It has been shown to exhibit better thermal insulation than the ones.   U.S. Pat. No. 4,454,248 softens a partially cured rigid foam and then crushes it. Method for producing rigid polyurethane foam which is allowed to expand, re-expand and then completely cured Is disclosed.   In co-pending application PCT / EP 9601594, a type of flexible polyurethane foam was opened. As shown, such foams have a major glass-rubber roll between -100 ° C and + 25 ° C. No transfer. In more quantitative terms, these forms are called E '_{-100 ° C}/ E '_{+25 ° C} The ratio indicates 1.3-15.0, preferably 1.5-10, most preferably 1.5-7.5. −100 ° C Tan in the temperature range of ~ 25 ℃_δmaxIs less than 0.2. Such foam core dense The degree is 4-30kg / m^ThreeAnd preferably 4 to 20 kg / m^Three(Measured by ISO / DIS845) Can fluctuate. Such foams are manufactured by crushing rigid foams.   The invention relates to a polyisocyanate (1), a hydroxyl value of at least 150 mg KOH / g and a Polyether polyols (2) having nominal hydroxyl functionality of 2 to 8, 10 Polyesters having a hydroxyl value of ~ 150 mg KOH / g and an average apparent hydroxyl functionality of 2-6 Hard polyurethane by reacting terpolyol (3) and water A method for producing a foam, comprising a polyisocyanate (1), a polyol (2), The amounts of polyol (3) and water are as follows: polyisocyanate (1), polyol (2), 55 to 80, 3 to 20, 10 to 30, and 2 to 6 parts by weight per 100 parts by weight of water (3) and water, respectively The reaction is performed at an isocyanate index of 102 to 200, preferably 102 to 150. Then, the polyisocyanate was added to the above-mentioned polyol (2), polyol (3) and water 1 Species, but include compounds having primary, secondary or tertiary nitrogen atoms. Reacting with one or more isocyanate-reactive compositions It relates to a method for producing a foam.   This improved process results in foams that are less thermally decomposed, The foam can be transferred to a large van (slab stock Produced as a foam having improved stability and low extractables can get.   The present invention particularly relates to a polyisocyanate (1) having a flatness of 70 to 300, preferably 70 to 150. Average equivalent hydroxyl functionality of 2-6, preferably 2-3, and low Polyether polyol (2) having an oxyethylene content of 75% by weight, 1000 Having an average equivalent weight of ~ 3000, an average apparent hydroxyl functionality of 2-3, preferably 2, and Construction: HO- (EO)_X-(PO)_Z-(EO)_Y-X [-O- (EO)_Y-(PO)_Z-(EO)_XH]_n               Equation 1 (Wherein, EO is an ethylene oxide group, and PO is a propylene oxide group. , X = 1-15, preferably 3-10, y = 0-6, preferably 1-4 , Z is an amount equivalent to the above-mentioned equivalent, n = 1 to 2, and X is 2 to 10 , Preferably a hydrocarbon group having 2 to 6 carbon atoms, or of the formula: -CH_Two-CH_Two -(O-CH_Two-CH_Two)_1-2-Is a group having) a polyether polyol (3) having A method for producing a rigid foam by reacting water, comprising the steps of: (1), the amount of polyol (2), the amount of polyol (3) and water are polyisocyanate (1), 55-80, 3-20, 1 per 100 parts by weight of polyol (2), polyol (3) and water, respectively 0 to 30 and 2 to 6 parts by weight, the reaction is 102 to 200, preferably 102 to 105 Performed with a cyanate index, the polyisocyanate, the polyol (2) , Polyols (3) and one or more types of water, containing primary, secondary or tertiary nitrogen sources. One or more isocyanate-reactive compositions not containing compounds having carboxylic acids Reacting with a substance.   Preferably, the amount of water is 3 to 5 parts by weight, calculated on the same basis. Like Alternatively, the weight ratio of water to polyol (3) is 0.1 to 0.4: 1, The weight ratio of Riol (2) + water is 0.9-2.5: 1. The obtained rigid foam core Density is 3 ~ 15kg / m^Three(ISO 845).   Furthermore, the present invention relates to a rigid foam thus obtainable, Method for producing a flexible foam by crushing a rigid foam, thus obtained Flexible foams, which contain components for producing these foams Reaction system, and the above polyether polyol (2), polyether polyol (3) and Water is added to each of 15 to 40, 45 per 100 parts by weight of polyol (2), polyol (3) and water. -75 and 5-20 parts by weight of a polyol composition provided that the primary, primary and The composition is free of compounds having a secondary or tertiary nitrogen atom. Further In addition, the present invention comprises a polyol (2), water and a phosphate (phsophate). In the composition, the amount of the polyol (2) and water is 100% by weight of the polyol (2) and water. 45 to 80 and 20 to 55 parts by weight per part, respectively, and the amount of phosphate is polyol (2) and 0.025-2.5% by weight calculated on the amount of water, provided that it is primary, secondary or tertiary The composition does not include a compound having a nitrogen atom.   Foams of the present invention have no major glass-rubber transition between -100 ° C and + 25 ° C . In more quantitative terms, these forms are between 1.3 and 15.0, preferably between 1.5 and 10 , Most preferably 1.5 'to 7.5'_{-100 ° C}/ E '_{+25 ° C}Shows the ratio. Soft foam core dense The degree is 3-20kg / m^Three(ISO 845).   In the present invention, the flexible polyurethane foam has at least one three-dimensional shape. At least 40%, preferably at least 50%, most preferably 55 to 85% ball rebound (measured according to ISO 8307), sag factor of at least 2.0 Crushed foam with (CLD 65/25) (measured according to ISO 3386/1). Preferably In the case of such a flexible foam, at 25 ° C., 500 kPa or less, more preferably 350 kPa Below, most preferably a Young storage modulus of 10 to 200 kPa (according to ISO / DIS 6721-5) Young's storage modulus measured by DMTA). Furthermore, such flexible foam Has a sag factor (CLD 65/25) of at least 3.5, most preferably 4.5 to 10 (IS O 3386/1). More soft fonts Preferably less than 55%, more preferably less than 50%, and most preferably less than 45%. Has full CLD hysteresis loss (ISO 3386/1).   In the present invention, the rigid polyurethane foam is less than 40% in the form rise direction. Full ball rebound resilience (excluding preflex conditions, Measure the rebound only once and prepare the specimen at 23 ± 2 ° C and 50 ± 5% relative humidity. Subject to ISO 8307) and / or in the form rise direction Measured CLD 65/25 sag factor less than 2.0 (excluding first load-unload cycle) With ISO 3386/1), provided that the sag factor is measured after Crushed foam; each 3-15kg / m^ThreeThe core density was measured. Such hard Quality Form E '_{-100 ° C}/ E '_{+25 ° C}Preferably, the ratio is between 1.3 and 15. In the present invention, I When SO 8307 and ISO 3386/1 are described for rigid foam, It shall be related to the above test including the conditions of writing.   The flexible polyurethane foam of the present invention comprises a polyisocyanate and a polyfunctional isocyanate. Anate-reactive polymer and foam to produce rigid polyurethane foam React under forming conditions and then crush this rigid polyurethane foam To manufacture. Furthermore, the present invention provides a method and a method for producing such a rigid foam. And a reaction system containing components for producing such foams.   For the purposes of the present invention, the following terms shall have the following meanings:   1) Isocyanate index or NCO index or index:   The ratio of NCO groups to isocyanate-reactive hydrogen atoms present in the formulation is expressed as a percentage and Is given as:  In other words, the NCO-index refers to the isocyanate-activity used in the formulation. The amount of isocyanate theoretically required to react with the amount of Represents the percentage of isocyanate actually used.   The isocyanate index used herein is an isocyanate component. And the actual foaming process involving isocyanate-reactive components. You have to keep in mind. Preliminary for the production of modified polyisocyanates Any isocyanate groups consumed in the step (pseudo- or semi-prepolymer and Including isocyanate-derivatives as referred to in the art as prepolymers) Or (e.g., to produce modified polyols or polyamines Any active hydrogen consumed in the preliminary stage (reacted with the Not taken into account when calculating the index. Free isocyanate present in the actual foaming stage Only anate groups and free isocyanate-reactive hydrogen (including those of water) Take into account.   2) Used herein for the purpose of calculating the isocyanate index. The expression "isocyanate-reactive hydrogen atom" is present in a reactive composition Refers to all active hydrogen atoms in the hydroxyl group; this is the isocyanate in the actual foaming process For the purpose of calculating the salt index, one hydroxyl group converts one active hydrogen One water molecule is considered to contain two active hydrogens Means that.   3) Reaction system: the polyisocyanate is one separate from the isocyanate-reactive component Combinations of components held in the above containers.   4) As used herein, the expression "polyurethane foam" uses a blowing agent. To react the polyisocyanate with the isocyanate-reactive hydrogen-containing compound. Cellular products, especially reactive foaming agents To form water (urea bond and carbon dioxide to form polyurea-urethane foam) Reaction between water and isocyanate groups) and isocyanate-reactive compounds Refers to a foam product obtained from a polyol.   5) In this specification, the term "average apparent hydroxyl functionality" refers to the Number average functionality of the initiator or initiators used in the reaction (active hydrogen source per molecule) Number of polyols or polyol compositions based on the assumption that Used to indicate functionality (number of hydroxyl groups per molecule), but in practice Often the ends are unsaturated and are often somewhat less.   6) The term "average" refers to the number average, unless stated otherwise.   Suitable organic polyisocyanates for use in the process of the present invention include: Aliphatic, cycloaliphatic, araliphatic and, preferably, aromatic polyols Socyanates, for example, in the form of their 2,4 and 2,6-isomers and mixtures thereof Le Endiisocyanates, 2,4'-, 2,2'- and 4,4'-isomers and their mixtures Diphenylmethane diisocyanate, diphenylmethane diisocyanate (MD I) and “coarse” or polymeric MDI (Polymethylene Polyphenylene Po Having two or more isocyanate functionalities, known as polyisocyanates) Mixture with oligomer, urethane, allophanate, urea, buret, cal Known MDIs containing bodimide, uretonimine and / or isocyanurate groups A process known in the art for producing rigid polyurethane foams, such as variants of The intention is given.   Toluene diisocyanate and diphenylmethane diisocyanate and / or Mixtures with polymethylene polyphenylene polyisocyanate may be used. 2.1 Polyisocyanates having an average isocyanate functionality of ~ 3.0, preferably 2.2-2.8 Most preferably, nates are used.   Using MDI, crude or polymeric MDI and / or liquid variants thereof Preferably, said variant is a uretonimine having an NCO value of at least 20% by weight And / or uretonimines and / or carbodiimide-modified polyisocyanates. And / or by introducing a carbodiimide group into the polyisocyanate group. Modified polyisocyanate having an NCO value of at least 20% by weight Such polyisocyanates are converted to hydroxyl functionalities of 2 to 6 and Obtained by reacting with one or more polyols having a molecular weight of 62 to 500.   Suitable polyether polyols (2) are fully described in the prior art, Examples include alkylene oxides such as ethylene oxide and / or It contains propylene oxide and 2 to 8 active hydrogen atoms per molecule. Reaction products with initiators that do not contain primary, secondary or tertiary nitrogen atoms. You. Suitable initiators include polyols such as ethylene glycol, die Tylene glycol, triethylene glycol, propylene glycol, dipropylene Lenglycol, butanediol, glycerol, trimethylolpropane, pe Includes antaerythritol, sorbitol and sucrose and mixtures of such initiators Can be Other suitable polyether polyols (2) include ethylene glycol , Diethylene glycol, propylene glycol, dipropylene glycol, Butanediol, glycerol, trimethylolpropane and the other initiators mentioned above No. Mixtures of such isocyanate-reactive compounds can be used as well . Most preferred polyols (2) have an average equivalent weight of 70-300, preferably 70-150. Having an average apparent hydroxyl functionality of 2-3 and at least 75% by weight of oxyethylene And those having an ionic content. Such most preferred polyols have an average equivalent weight Having an equivalent weight of less than 70, under the condition that is within the range of 70 to 300, Polyols that meet other criteria with respect to value and oxyethylene content. Such most preferred polyols are known per se and are commercially available.   Polyether polyols (3) are generally known, alkylene oxide Such as ethylene oxide and / or propylene oxide per molecule Contain 2 to 6 active hydrogen atoms and do not contain primary, secondary or tertiary nitrogen atoms. Reaction products with different initiators. Suitable initiators include ethylene glycol , Diethylene glycol, triethylene glycol, propylene glycol , Dipropylene glycol, butanediol, glycerol, trimethylol There is a mixture of lopan, pentaerythritol, sorbitol and such initiators .   The most preferred polyether polyols (3) are according to formula 1 above. . Those having an apparent hydroxyl functionality of 3 include glycerol and / or trimethylo. Ethoxylation of initiators, which are propane-like triols, followed by propoxylation , By re-ethoxylation. Those having an apparent hydroxyl functionality of 2 , Ethylene glycol, diethylene glycol and / or triethylene glycol Ethoxylation, followed by propoxylation, re-ethoxylation; or Ethylene glycol, diethylene glycol and / or triethylene glycol Ropoxylation followed by ethoxylation; or with 4 to 15 oxyethylene groups Propoxylation of polyoxyethylene polyol followed by ethoxylation I can do it. Mixtures of such most preferred polyols may also be used. Equation 1 If it does not exceed 30% by weight based on the weight of the polyol, it is not essential, Other polyols may be used with the most preferred polyols of Formula 1. Equation 1 Such polyols are commercially available (e.g., Imperial Chemical Industr ies PLC Daltocel F 430).   To make the foam, water is used as a blowing agent. However, water If the amount is not sufficient to obtain a foam of the desired density, Use of various pressures, air, N_TwoAnd CO_TwoUse of gas such as chlorofluorocarbon More commonly used for hydrocarbons, hydrofluorocarbons, hydrocarbons and fluorocarbons Use of a blowing agent, which reacts with other reactive blowing agents, i.e., any components in the reaction mixture. The use of agents that liberate gases that cause the mixture to bubble through the reaction, and phosphorylation Carbodiimides, such as oxides-lead to gas formation, such as the use of a promoting catalyst Any other method of producing polyurethane foam through the use of a catalyst to promote the reaction Known methods can be used. Combination of these methods to produce foam Can also be used. The amount of blowing agent can vary over a wide range and is mainly the desired density Depends on. As liquid at below ambient, ambient or elevated temperature, and as vapor Water can be used. A preferred combination of blowing agents is water and CO_TwoAnd CO_TwoIs The components for the production of foam in the mixing head of the equipment for producing the One of the nate-reactive components, and preferably, the polyisocyanate is an isocyanate Add to the polyisocyanate before contacting the nate-reactive component.   Cyclic polyisocyanates, especially aromatic polyisocyanates, more particularly MDI Or, when using polymethylene polyphenylene polyisocyanate, The content of cyclics in the foam, especially the content of aromatic residues, is controlled by the conventional soft polyurethane foam. Relatively high compared to the ohm. The foam of the present invention is based on the weight of the foam. And preferably in an amount of 30 to 56% by weight, most preferably 35 to 50% by weight. It has a benzene ring content derived from socyanates. Poly containing benzene ring Oars, polymer polyols, flame retardants, chain extenders and / or fillers As it can be used, the total benzene ring content of the flexible foam can be high and the Fourier 30 to 70% by weight, most preferably calibrated and measured by conversion infrared analysis. Or in the range of 35-65% by weight.   Under the condition that they do not contain primary, secondary or tertiary nitrogen atoms. Besides isocyanates, isocyanate-reactive compounds and blowing agents, polyurethane One or more auxiliaries or additives known per se for the production of foams can be used. Such optional auxiliaries or additives include cell stabilizers or surfactants (e.g., , Siloxane-oxyalkylene copolymers and polyoxyethylene polyoxy Propylene block copolymers), urethane / urea catalysts (eg, tin compounds, An example For example, dibutyltin dilaurate, especially tin octoate, and / or phosphate (eg, If NaH_TwoPO_FourAnd NaHPO_Four), And a flame retardant such as a halogenated alkyl phosphate (For example, trischloropropyl phosphate), antioxidants (tertiary nonyl phthalate) Enols), antistatic agents, UV stabilizers, antimicrobial and anti-bacterial compounds and fillers ( Latex, TPU, silicate, barium and calcium sulfate, chalk and glass Fibers or beads).   Preference is given to using catalysts which promote the formation of urethane and / or urea groups, In particular, it is preferred to use tin octoate, optionally with other catalysts. catalyst The amount is calculated as 0.1 based on the weight of all ingredients used to form the foam. -5% by weight, preferably 0.1-3% by weight; of tin octoate The amount varies from 0.1 to 3% by weight, preferably from 0.1 to 2% by weight, calculated on the same basis. Can be   During operation of the method for producing the rigid foam of the present invention, a known one-shot, pre- Use of polymer or semi-prepolymer methods with conventional mixing methods Rigid foam for slabstock, fabric and in-situ foaming applications Molded articles, including foam, spray foam, frothed foam Or other materials (eg, hardboard, plasterboard, plastic, paper Or metal) or other laminates with foam layers.   In many applications, the primary polyisocyanate and each of the isocyanate-reactive components Ingredients for polyurethane production in a pre-blended formulation based on It is convenient to combine them. Isocyanate in the form of a solution, emulsion or dispersion G-In addition to the reactive compounds (2) and (3), especially contains auxiliaries, additives and foaming agents Isocyanate-reactive components may be used. Isocyanate-reactive component added The polyisocyanate is independently provided as two or more compositions containing an agent and an auxiliary. One composition comprising, for example, water and polyol (2); Other components including polyol (3), catalyst and antioxidants from separate storage tanks To the mixing head of the foam manufacturing equipment for mixing the polyisocyanate. Can be.   Rigid foam reacts the above components and then the foam no longer rises Manufactured by foaming to the extent possible.   After rise, curing of the foam can be continued for as long as desired. General In general, a curing time of 1 minute to 24 hours, preferably 5 minutes to 12 hours, will be sufficient. Desired Thus, curing can be performed at an elevated temperature. Subsequently, the foam may be crushed. However, it is preferred to cool the resulting rigid foam to below 80 ° C. before crushing. New The rigid foam (ie before crushing) preferably has a core density of 3 to 15 kg / m^Three(I SO 845).   The rigid foam produced (ie, before crushing) has a substantial amount of open cells. Hard Preferably, the cells of the foam are mainly independent. Crushing can be accomplished by any known method and method. And any known means. Crush, for example, flat or preformed Depending on the surface, apply mechanical force on the foam or apply various external pressures It can be implemented by doing.   In most cases, the size of the foam in the crush direction by 1-90%, preferably 50-90% Sufficient mechanical force to reduce is preferred. Repeat crushing if desired. And / or in different directions of the foam. Crushed by the bow The rebound resilience increases significantly in the crushing direction. Crushing increases foam density obtain. In most cases, this increase does not exceed 30% before collapse.   The foam may collapse in the form rise direction. Collapse the form rise direction When carried out perpendicular to, a special foam is obtained; then highly anisotropic A foam having a porous cell structure is obtained.   Above all, it depends on the foam density, foam stiffness and the type of crushing equipment used It is difficult to give a more accurate orientation for crushing, Those skilled in the art will recognize that the above guidance, particularly the following examples, Be familiar with the crushing phenomena of polyurethane foam, it is possible to determine the means I think. After crushing, foam to reduce the density increase caused by crushing Can be subjected to a heat treatment. This heat treatment is performed at 70 to 200 ° C, preferably 90 to 180 ° C. C. for 0.5 minutes to 8 hours, preferably 1 minute to 4 hours.   The crushing increases the ball rebound resilience at least in the crushing direction. Increase is small At least 10%. After crushing and, in some cases, heating, a new material with outstanding properties A flexible foam is obtained. Despite the fact that the foam is flexible, As described above, the Young's storage modulus E 'was observed over the temperature range of -100 ° C to + 25 ° C No significant fluctuation is shown. Oxygen in foams made from aromatic polyisocyanates Preferably, the index is 20 or more (ASTM 2863). At 25 ° C Young storage modulus is 500 kPa or less, preferably 350 kPa or less, most preferably 10 to 200kPa, sag factor (CLD 65/25, ISO 3386/1) at least 2.0, good Preferably at least 3.5, most preferably 4.5-10. Form CLD hysteresis The lysis loss value is less than 55%, preferably less than 50% [Formula:(Where A and B are measured according to ISO 3386/1, with load (A) and without load (B) Calculated under the stress / strain curve). In addition, these files The ohm is very high, as measured by a lateral elongation study under foam compression. At low or negative Poisson's ratio. Finally, in the form Compression set values are generally low, preferably less than 40% (ISO 1856 Method A, ).   Tg^hIf the foam is not too high, the foam will be a thermoset process to make the part Could be used. For such thermosetting applications, the Tg of the foam^hBut , 80-180 ° C, most preferably 80-160 ° C. further, Produced by using relatively low amount polyols with low molecular weight Forms are small or invisible Tg due to DMTA^h(Tg^hOf elastic modulus in Is small or the modulus varies gradually until the foam is pyrolyzed) Shown; such foams can also be used for thermosetting.   Furthermore, the foam has good resilience, tear strength, even at very low densities Compression hardness (without external filler) along with hardness and durability (fatigue resistance) Shows good load-bearing properties such as compression hardness value. Conventional soft Foams often use large amounts of filler to obtain sufficient load-bearing properties. Must be used. Such a large amount of filler increases the viscosity. Processing is hindered.   The foam of the present invention is generally used for furniture, automobiles, aircraft seats and mattresses. As a cushion material, as a carpet backing, with a diaper hydrophilic foam And as a packaging foam, sound insulation and vibration isolation for automotive applications (vibration isolati on) It can be used as a form. The foam of the present invention may further comprise, for example, a molded article. Used with other conventional flexible foams to form any foam composite Such a composite may be a conventional soft foam in the presence of the foam of the present invention. Forming the foam in a mold with the components for producing the Ingredients for producing rigid foams in a mold in the presence of conventional flexible foams By forming the rigid foam and subsequently crushing the molded article thus obtained Can also be manufactured. Furthermore, the foam of the present invention can be used as a textile cover, As a cover for other types of sheets, carpet underlay or felt-with replacement It can be used by applying the so-called flame bonding method The foam can be glued to an il, carpet or other sheet. this In this regard, the foams of the present invention can be used, for example, with a limited thickness of about 1 cm or less. It is important to note that the material is suitable for cutting. Furthermore, the present invention The foam may be used as insulation around pipes and containers.   The present invention is illustrated by the following examples.Example 1 (Comparative example)   56.6% by weight of polymer MDI having an NCO value of 30.7% by weight and an isocyanate functionality of 2.7 Parts, NCO value 31% by weight, isocyanate functionality 2.09, uretonimine content 17% by weight Of uretonimine-modified MDI containing 43.3 parts by weight of uretonimine and 20% by weight of 2,4'-MDI Thereby, a polyisocyanate mixture was produced. Polye having a molecular weight of 200 32.2 parts by weight (pbw) of ethylene glycol, 4.5 pbw of ethylene glycol, apparent functionality 2 , Diethylene glycol as initiator, EO content (other than initiator) 20.2% by weight 42.6 pb EO / PO polyol with tipped) and 30 mg KOH / g hydroxyl value w, diethanolamine 5.5 pbw, water 14.5 pbw and di-butyl-tin-dilaurate 0.7 An isocyanate-reactive composition was prepared by mixing the pbw. This composition The thing was an emulsion.   106.1 pbw of polyisocyanate mixture and isocyanate-reactive composition (isocy Anate Index 75.5) 46.9 pbw and the Heidolph ™ mechanical mixer The mixture was mixed for 13 seconds at a speed of 5000 revolutions / minute (rpm) using a mixer. After mixing, reaction mixing The material was poured into an open 5 liter bucket and allowed to react. Pour reaction mixture into bucket Before release, the release agent Desmotrol ™ D-10RT was applied to the inner wall of the bucket. Form 2.5 minutes after the rise has stopped (form rise time 70 seconds), Removed from bucket and allowed to cool at ambient temperature. Rigid polyurethane foam obtained Was. Core foam samples were cut from the center of the foam for characterization . Core density is 11kg / m^Three(ISO 845).   The experiment was performed on a Komet high pressure, multi-stream dispenser using a total of 3 kg of material. Repeated. The rigid foam exhibited excessive thermal degradation.Example 2 (Comparative example)   Three isocyanate-reactive blends (blends A, B and C) were prepared. Blend A comprises 200 pbw of the EO / PO polyol of Example 1 and “DABCO” T9 (AIR PRODUCTS , DABCO was manufactured by mixing with 6.5 pbw. Blend B 75.5 pbw of polyethylene glycol having a molecular weight of 200 and “IRGANOX” 5057 (Ciba- A substituted diphenylamine antioxidant commercially available from Gcigy Ltd., IRGANOX is a trademark) 5.56p bw. Blend C is triethylene glycol 23. Made by mixing 5pbw, water 40.0pbw and monobasic sodium phosphate 0.6pbw did.   166.1 g of Blend A, 65.2 g of Blend B, 51.6 g of Blend C and the isocyanate of Example 1 Add 617.1 g of anate blend (isocyanate index 100) to “Ytron” (trademark) Mark) Mixing was performed at 3500 rpm for 13 seconds using a mechanical mixer. After mixing Open the reaction mixture 50 × 50 × 30cm^ThreePoured into wooden mold. Before pouring the mixture into the wooden mold Then, the inner wall was covered with paper. One hour after foaming stops The foam was removed from the mold and allowed to cool at ambient temperature. The rigid foam was cut as in Example 1. Core density is 13kg / m^Three(ISO 845) Was. No discoloration of the rigid foam was observed, and the extract amount was 7.3% by weight.   This experiment was identical except that a slightly different isocyanate blend was used. This was repeated using a Komet high pressure, four-way dispenser. For this purpose, Four blends of blends D, E, F and G were produced. Blend D is from Example 1. 58.2kg of EO / PO polyol and IRGANOX 5057 1.88kg Made from Blend E comprises 6792 g of the EO / PO polyol of Example 1 and DABCO T9 2208 g. Blend F is a polyethylene rubber with a molecular weight of 200. Recol 4868g, triethylene glycol 1515g, water 2579g and sodium phosphate monobasic And 39 g of Pt. Blend G is the polymer MD of Example 1. I 60.0 kg and 51.9 kg of the uretonimine-modified isocyanate of Example 1 were mixed. And manufactured by.   Mix streams D, E, F and G in a weight ratio of 18.56 to 2.65 to 13.96 to 76.70, respectively. Set the measuring instrument, 3 kg of foam, open paper-lined 50 × 10 0 × 30cm^ThreeManufactured in wooden molds. The isocyanate index reached 100. Rigid foam has a core density of 13 kg / m^Three(ISO 845) and extract amount 12.4% by weight Was. In addition, the foam core showed some discoloration.Measurement of foam extract   Continuous extraction using Soxhlet apparatus and methanol as solvent The physical quantity was measured. The equipment is a 500 ml-type flask, a Soxhlet apparatus and a Dimroth Consists of a cooler. 0.3cm of 3-4g foam sample^ThreeCut into pieces and extract cylinder It was placed in filter paper and mounted on a Soxhlet apparatus. Extract with 300 ml methanol Was. The methanol in the flask was heated by an oil bath set at a temperature of 140 ° C. 3 O'clock After refluxing, methanol was removed from the filtrate using a rotary evaporator . Subsequently, the weight of the residue in the flask was measured. Extract the amount of extract It was calculated from the weight of the sample and the amount of extracted material and expressed as% by weight.Example 3 (Comparative example)   Two isocyanate-reactive blends (blends A and B) were prepared. Bren A is 30 pbw of the EO / PO polyol of Example 1, 0.3 pbw of "DABCO" T9 and 1-methyl-1-O By mixing 0.3 pbw of xo-phospholene (carbodiimide catalyst manufactured by Hoechst) Manufactured. Blend B is composed of 11.3 pbw polyethylene glycol with a molecular weight of 200, Mix 1.95 pbw of tanolamine, 1.58 pbw of ethylene glycol and 4.5 pbw of water. And manufactured by.   26.9 g of Blend A, 17.3 g of Blend B and the isocyanate blend of Example 1 108.6g (isocyanate index 123) with “Heidolph” Mechanical Mix In a sir, the mixture was mixed at a speed of 5000 rpm for 13 seconds. After mixing, the reaction mixture is opened 5 liters open. The mixture was poured into a torn bucket and reacted. 1 hour after stopping foaming (form The foam was removed from the bucket and allowed to cool at ambient temperature. Core density 16kg / m^Three(ISO 845) rigid polyurethane foam was obtained. Total reflection absorption Fourier transform infrared analysis showed the presence of carbodiimide groups (2140 cm^{- 1} Signal).   No signs of discoloration of the foam core were observed. This experiment was performed using the YT of Example 2. RON mixer and mixing conditions, paper-lined 50 × 50 × 30cm^ThreeThe dimensions of wooden This was repeated with 1.3 kg of material using a mold. Core density 13.8kg / m^ThreeThe rigid foam is obtained Discoloration was observed in the center of the van.Example 4   In this example, 58.2 kg of the EO / PO polyol of Example 1 was blended with Blend D of Example 2. And IRGANOX 1010 (a structural hindered phenol antioxidant manufactured by Ciba-Geigy Ltd., I RGANOX is replaced by Blend H made by blending 1.88 kg) I got it.   Blends H, E, F and G are mixed at a weight ratio of 18.56 to 2.65 to 13.96 to 76.70, respectively. Set the dispenser so that the 3kg of foam was open paper lining 50 × 100 × 30cm^ThreeManufactured in wooden molds. Isocyanate index reaches 100 did. Rigid foam has a core density of 12.7 kg / m^Three(ISO 845) and extract amount 11.6% by weight Had. The foam core did not show any discoloration. Flow G weight ratio of 78.2 , 79.8 and 81.3, respectively, increasing the isocyanate indexes 102, 404 and 10 respectively. Six foams were produced. Rigid foam has a core density of 13.3, 12.3 and 13.4 kg / m^Three(ISO 845) and the extract amounts reached 7.4, 1.5 and 3.4% by weight respectively. this None of these foams showed any discoloration.   Foams having isocyanate indices 102, 104 and 106, Rise using the installed INSTRON (INSTRON is a trademark) mechanical tester Once at 100mm / min in the direction (70% CLD), then 500mm / min in the rise direction of the foam By crushing 15 times per minute (70% CLD of height after initial compression) Crushed.   After crushing, there is no major glass-rubber transition between -100 ° C and + 25 ° C. A flexible foam was obtained. Isocyanate index 102 104 106 Core density after crushing (ISO 845, kg / m^Three) 14.7 13.3 16.8 Young storage modulus ratio (E '_{-100 ° C}/ E '_{+25 ° C}) 2.7 2.5 2.5 (ISO / DIS 6721-5) Young storage modulus (25 ° C) (kPa) 215 166 192 (ISO / DIS 6721-5) Benzene content (% by weight: calculated value) 43.3 44.1 45.2 Ball rebound resilience (%, ISO 8307) 53 55 53 CLD-40% (kPa, ISO 3386/1) 5.5 5.6 7.5 Sag factor (CLD 65/25, ISO 3386/1) 5.7 4.8 8.6

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) B29K 105: 04 (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG) , AP (GH, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, EK, EE, ES, FI, GB, GE, GH, HU, ID, IL, I S, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO , RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW

Claims (1)

[Claims]   1. Polyisocyanate (1), hydroxyl value at least 150 mg KOH / g and average mika Polyether polyol (2) having hydroxy functionality of 2 to 8, 10 to 150 mg KOH / g Polyether polyol having a hydroxyl value and an average apparent hydroxyl functionality of 2 to 6 (3 ) And a method for producing a rigid polyurethane foam by reacting water. The amount of polyisocyanate (1), polyol (2), polyol (3) and water is Per 100 parts by weight of polyisocyanate (1), polyol (2), polyol (3) and water The reaction is 55 to 80, 3 to 20, 10 to 30 and 2 to 6 parts by weight, respectively. The polyisocyanate was used at the above-mentioned polyol (2 ), One or more polyols (3) and water, and primary, secondary or tertiary nitrogen Reaction with one or more isocyanate-reactive compositions not containing compounds having atoms A process for producing the polyurethane foam.   2. The method of claim 1, wherein the index is between 102 and 150.   3. Polyol (2) has an average equivalent weight of 70 to 300 and an average apparent hydroxyl functionality of 2 to 6 And having an oxyethylene content of at least 75% by weight. Method.   4. Polyol (2) has an average equivalent weight of 70-150 and an average apparent hydroxyl functionality of 2-3 4. The method of claim 3, having a valency.   5. The polyol (3) has an average equivalent weight of 1,000 to 3,000 and an average apparent hydroxyl group of 2-3. Efficacy and structure: HO- (EO)_X-(PO)_Z-(EO)_Y-X [-O- (EO)_Y-(PO)_Z-(EO)_XH]_n              Equation 1 (Wherein EO is an ethylene oxide group and PO is a propylene oxide group , X = 1 to 15, y = 0 to 6, and z is an amount equivalent to the above equivalent. , N = 1 to 2, and X is a hydrocarbon group having 2 to 10 carbon atoms Or the formula: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-2Which is a group having-). The method described in.   6. An apparent hydroxyl functionality of 2, x = 3-10, y = 1-4, n = 1 and X is a hydrocarbon group having 2 to 6 carbon atoms, or Is the formula: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-2- The method according to claim 5, which is a group having the formula:   7. Producing foams with catalysts that enhance the formation of urethane and / or urea groups 0.1 to 5% by weight, calculated based on the weight of all ingredients used to 7. The method according to claims 1 to 6 for use.   8. Tin octoate, based on the weight of all components used to make the foam The process according to claim 7, wherein the amount is used in an amount of 0.1 to 3% by weight, calculated as   9. Crushing rigid polyurethane foam produced according to claims 1 to 8. For producing a flexible polyurethane.   10. A rigid polyurethane foam obtainable by the method according to claim 1. Ohm.   11. Core density 3 ~ 15kg / m^ThreeThe rigid polyurethane according to claim 10, having: Form.   12. A flexible polyurethane foam obtainable by the method according to claim 9. M   13. 13. The method according to claim 12, which has no major glass-rubber transition between -100 ° C and + 25 ° C. The flexible polyurethane foam as described.   14. E 'of 1.3-15_{-100 ° C}/ E '_{+25 ° C}13. The soft poly according to claim 12, having a ratio. Urethane foam.   15. 15. The softener according to claim 12, having a resilience of at least 50%. Quality form.   16. The soft foam of claims 12 to 15 having a resilience of 55 to 85%. Home.   17． Core density 3-20kg / m^ThreeThe soft foam according to any one of claims 12 to 16, which has M   18. Has a benzene ring content of 30-70% by weight based on the weight of the foam The flexible foam according to any one of claims 12 to 17.   19. Has a benzene ring content of 35-65% by weight based on the weight of the foam The flexible foam according to any one of claims 12 to 18.   20. 20. The soft disk of claim 12 having a sag factor of at least 2.0. Ohm.   21. 21. The soft disk of claim 12 having a sag factor of at least 3.5. Ohm.   22. The flexible foam of claims 12-21, having a sag factor of 4.5-10. .   23. It has a Young's storage modulus of 500 kPa or less at 25 ° C. 3. The flexible foam according to 2.   24. A material having a Young's storage modulus of 10 to 200 kPa at 25 ° C. 4. The flexible foam according to 3.   25. Polyisocyanate (1), hydroxyl value at least 150 mg KOH / g and average Polyether polyol (2) having a crosslinked hydroxyl functionality of 2 to 8, 10 to 150 mg KOH / g Polyether polyol having a hydroxyl value and an average apparent hydroxyl functionality of 2 to 6 (3) and a reaction system containing water, polyisocyanate (1), polyol (2), The amounts of polyol (3) and water are as follows: polyisocyanate (1), polyol (2), 55 to 80, 3 to 20, 10 to 30, and 2 to 6 parts by weight per 100 parts by weight of water (3) and water, respectively In an amount such that the isocyanate index becomes 102 to 200, All (2), polyol (3) and water have primary, secondary or tertiary nitrogen atoms. The reaction system does not contain any of the following compounds.   26. The reaction system according to claim 25, wherein the index is from 102 to 150.   27. Polyol (2) has an average equivalent weight of 70 to 300 and an average apparent hydroxyl functionality of 2 to 6 27. The composition according to claim 25, which has an oxyethylene content of at least 75% by weight. The described reaction system.   28. The polyol (2) has an average equivalent weight of 70 to 150 and an average apparent hydroxyl group of 2 to 3 28. The reaction system according to claim 27 having potency.   29. Polyol (3) has an average equivalent weight of 1,000 to 3,000 and an average apparent hydroxyl group of 2-3 Functionality and structure: HO- (EO)_X-(PO)_Z-(EO)_Y-X [-O- (EO)_Y-(PO)_Z-(EO)_XH]_n               Equation 1 (Wherein EO is an ethylene oxide group and PO is a propylene oxide group , X = 1 to 15, y = 0 to 6, and z is an amount equivalent to the above equivalent. , N = 1 to 2, and X is a hydrocarbon group having 2 to 10 carbon atoms Or the formula: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-2Which is a group having-) A reaction system according to 25 to 28.   30. An apparent hydroxyl functionality of 2, x = 3-10, y = 1-4 , N = 1, and X is a hydrocarbon group having 2 to 6 carbon atoms, or Or expression: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-2- 30. The reaction system according to claim 29, which is a group having   31. A catalyst that promotes the formation of urethane and / or urea groups is 0.1 to 5% by weight, calculated on the weight of all ingredients used to make The reaction system according to claims 25 to 30, which is used.   32. Tin octoate is based on the weight of all ingredients used to make the foam. 32. The reaction system according to claim 31, which is used in an amount of 0.1 to 3% by weight, calculated as a weight.   33. A hydroxyl value of at least 150 mg KOH / g and an average apparent hydroxyl functionality of 2-8 Polyether polyol (2) having a hydroxyl value of 10 to 150 mg KOH / g and average mika Polyether polyol (3) having hydroxyl functionality of 2 to 6 and water 15 to 40, 45 to 75 and 5-2, respectively, per 100 parts by weight of water (2), polyol (3) and water. 0 parts by weight, excluding compounds having primary, secondary or tertiary nitrogen atoms A polyol composition.   34. Polyol (2) has an average equivalent weight of 70 to 300 and an average apparent hydroxyl functionality of 2 to 6 34. The method according to claim 33, having an oxyethylene content of at least 75% by weight. A polyol composition.   35. The polyol (2) has an average equivalent weight of 70 to 150 and an average apparent hydroxyl group of 2 to 3 34. The polyol composition according to claim 33 having potency.   36. Polyol (3) has an average equivalent weight of 1,000 to 3,000 and an average apparent hydroxyl group of 2-3 Functionality and structure: HO- (EO)_X-(PO)_Z-(EO)_Y-X [-O- (EO)_Y-(PO)_Z-(EO)_XH]_n (Wherein EO is an ethylene oxide group and PO is a propylene oxide group , X = 1 to 15, y = 0 to 6, and z is an amount equivalent to the above equivalent. , N = 1 to 2, and X is a hydrocarbon group having 2 to 10 carbon atoms Or the formula: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-233 to 34. 36. The polyol composition according to 35.   37. An apparent hydroxyl functionality of 2, x = 3-10, y = 1-4 , N = 1, and X is a hydrocarbon group having 2 to 6 carbon atoms, or Or expression: -CH_Two-CH_Two-(O-CH_Two-CH_Two)_1-2- 37. The polyol composition according to claim 36, which is a group having the formula:   38. A catalyst that promotes the formation of urethane and / or urea groups is 0.1 to 5% by weight, calculated on the weight of all ingredients used to make 38. The polyol composition according to claims 33 to 37 for use.   39. Tin octoate is based on the weight of all ingredients used to make the foam. 39. The polycarbonate according to claim 38, used in an amount of 0.1 to 3% by weight, calculated as a weight. Composition.   40. A composition comprising a polyol (2), water and a phosphate, wherein the composition comprises the polyol (2) and The amount of water is 45 to 80 and 20 to 55 weight per 100 parts by weight of polyol (2) and water, respectively. Parts, the amount of phosphate is 0.025 calculated on the basis of the amount of polyol (2) and water. -2.5% by weight, not containing primary, secondary or tertiary nitrogen atoms object.